Proceeding of Annual/Fall Meetings of the Japan Petroleum Institute

Today, alkylation process becomes very important from the viewpoint of environmental problems. Alkylation is a process to produce alkylate from isobutene and light olefine, which are obtained as a by-product in catalytic cracking, and reforming. Alkylate is the superior gasoline that does not contain benzene and sulfur at all. HF and H₂SO₄ are used as a catalyst in the industrialized process. However, the process using a liquid acid is not an industrially good process because both the liquid acid has the strong toxicity, and causticity. Thus, the alkylation process where the solid acid is used is widely studied in recent years. Especially, the zeolite is paid to attention as a new catalyst of the alkylation, because it has not toxicity, causticity, and is cheaper. However, it is difficult to use the zeolite as a catalyst of the industrial process for rapid deactivation. Therefore, in this study, the purpose is a search for the condition and the catalyst that suppresses the deactivation, and generates the C8 paraffin selectively.

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Slurry phase hydrocracking of hevy oil was carried out by using pulverized Mo catalyst, and the product oil was separated into toluene-insolubles, distillate and residue. The effect of recycling use of toluene-insolubles and residue on hydrocracking behavior and product quality was investigated.

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We have reported that the coke yields at heavy oil thermal cracking could be depressed with the pretreatment for relaxation of asphaltene aggregation with aromatic solvents. Recently, we studied the effect of the pretreatment at hydrocracking and hydrotreating of heavy oils. With the autoclave experiments, it was demonstrated that coke yields was depressed at hydrotreating and desulfurization was accelerated at hydrotreating with the pretreatment.

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It has been reported that the addition of citric acid on Co-Mo/B₂O₃/Al₂O₃ catalysts by a post-treatment considerably increases the HDS activity to the maximum potential activity compared with a simultaneous impregnation method. With the post-treatment, citric acid consumes already dispersed CoMoO₄ and polymolybdate species and thus increases the amount of Co-Mo-S after sulfidation. It seems that the effect of citric acid addition is greater for the calcined Co-Mo catalysts. In the present study, therefore, we investigated effect of calcination temperature of Co-Mo/B₂O₃/Al₂O₃ catalysts with the addition of citric acid by a post-treatment. Several characterizations were conducted in order to get the physicochemical properties of the prepared catalysts. It is shown that the HDS activity of the post-treatment Co-Mo/B₂O₃/Al₂O₃ is increased up to the calcination temperature of 500 deg. Celsius, the optimum temperature, suggesting that the large amount of well dispersed CoMoO₄ is formed while the sintering process occurs with a higher calcination temperature. Moreover, it is found that the HDS activity of Co-Mo/B₂O₃/Al₂O₃ catalysts is independent of the pH value on the citric acid addition. Co-Mo/Al₂O₃ catalysts were also investigated.

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